TW200923005A - Moisture-curable compositions, and a process for making the compositions - Google Patents

Abstract

Compositions useful as coatings for automobile power cables comprise a combination of moisture-crosslinkable, silane-grafted ethylene polymers in combination with a non-halogenated flame retardant. The ethylene polymers are a combination of at least one ethylene polymer with a density of 0.910 g/cc or greater and at least one ethylene polymer with a density less than 0.910 g/cc. The non-halogenated flame retardant is typically hydrated metallic filler, e. g., aluminum trihydrate. These compositions meet SAE J-1128 and Daimler Chrysler MS-8288 specifications, exhibit good shelf-life stability, and are useful in other automotive cable applications, such as ISO-6722.

Description

200923005 IX. INSTRUCTIONS: I: Inventor's technical field 3 Cross-references to related applications [0001] This application claims US Provisional Patent Application No. 60/974,562 filed on September 24, 2007. The priority of this application is hereby incorporated by reference in its entirety. FIELD OF THE INVENTION [0002] The present invention relates to moisture curable compositions. In one aspect, the invention relates to a moisture curable composition comprising a polyolefin, and in another aspect, the invention further comprises an unhalogenated flame retardant, a cross-linking The agent is associated with such a composition of a free radical initiator. In still another aspect, the invention is related to a method in which decane is grafted onto an olefin polymer in situ and in the presence of alumina trihydrate. In another aspect, the invention is related to a cable insulation layer made from the moisture curable composition 15. BACKGROUND OF THE INVENTION [0003] Insulating sheaths for power cables used in the automotive industry must have a good balance between mechanical and fire resistant properties. With regard to this mechanical property, 20 is typically provided by a crosslinked polyolefin such as polyethylene grafted with decane. With regard to the fire protection properties, it is typically provided by combining with a polymer of a flame retardant. The reagent may be halogenated or non-halogenated, and is preferably, for example, magnesium hydroxide, alumina trihydrate (ATH), talc, and the like. 200923005 100041 The composition of the insulating sheath that can be used to form the power cable can have many specific examples. U. The composition may also contain scaly and black spots. [0〇〇5] Another specific example is USP 4,921,916, which describes a method for making a parent-linked product of a non-fluorinated fire retardant by first forming a halogen-free composition. The basic component is at least a filler, an ethylene copolymer, a monodecane, a free radical grafting initiator, and a stanol 10 condensation catalyst. The radical initiator has a half-life of less than one minute at a temperature 25 ° C lower than the decomposition temperature of the filler. The grafting temperature is at least 25 〇c lower than the decomposition temperature of the filler. The polymer used in this specific example is ethylene/ethyl acrylate (EEA), very low density polyethylene (VLDPE), and acetonitrile/propylene/diene monomer (EpDM). [0006] Another specific example is USP 6,703,435 B2, which describes the production of a crosslinkable polymerization by mixing a thermoplastic base polymer containing ATH with a carrier polymer containing decane and a peroxide. The method of matter is to be below 165. (The temperature at which a monodecane crosslinkable compound is produced. The preferred peroxide uses a decomposition temperature of less than 165. The specific example 20 uses polyethylene and is grafted with maleic anhydride. Polymers of polyethylene. [0007] Other examples include usp 4, 732, 939, 5, 883, 144 and 5, 312, 861 ', and U.S. Patent Application Publication Nos. 2003/0134969 and 2003/0114604, and EP 0426073, 0365289 and 0245938. 200923005 100081 The composition used in automotive power cable applications must comply with an industry standard such as SAE J-1128 and/or Daimler Chrysler MS 8288. This SAE standard requires - is used in the regulation of vehicle electrical systems The surface must be used in a direct current (or 25 volt AC) with a nominal voltage of 60 volts or less under normal exposure to limited liquid and physical tests. The Daimler Chrysler MS The 8288 standard requires that the wire insulators have good ductility and heat resistance at 15 GT. [00〇9] USP 6,326,422 describes that the SAE j_1128 can be crosslinked with radiation 10 The composition and the cable application to which it is applied. The composition comprises an ethylene copolymer, a hydrated inorganic filler, an alkoxydecane, and a salt of a monohydrogen thiamidazole compound. Some patents have been described for sae A composition that can be crosslinked by peroxide, as used in J-1128, for example

EP 0 062 187 and USP 5, 225, 468, 5, 955, 525 and 6, 197, 864, USP 15 5, 401, 787 describe a moisture-curable composition of a flame retardant for use in SAE J-1128, the composition comprising (a) a decane copolymer, b) a halogenated carboxylic acid anhydride, and (c) antimony trioxide. SUMMARY OF THE INVENTION The invention of the present invention comprises a specific combination of a wet-crosslinkable polymer and a non-halogenated flame retardant. These compositions conform to the specifications of SAEJ-1128 and Daimler Chrysler MS-8288, have good shelf life stability, and can be used in other automotive cable applications such as ISO-6722. [0011] In a first specific example, the present invention is a composition comprising: [0012] 1. At least one density of 0.910 grams per cubic centimeter (g/cc) or more The decane grafted ethylene polymer; 5 [0013] 2 - at least one second decane grafted ethylene polymer having a density of less than 0.910 g/cc; and [0014] 3. At least one non-halogenated flame retardant. [0015] The decane system grafted to the ethylene polymer is typically derived from monovinyl decane, and the non-halogenated flame retardant is typically a metal hydrate. The density of the first and second decane-grafted ethylene copolymers is the density of the ethylene copolymer prior to grafting, and the first and second decane-grafted copolymers are Separation and differentiation, not the various parts of the multimodal copolymer. The composition may comprise, for example, one or more of the following additional compositions: an antioxidant, a light stabilizer, an inert filler, a 15 compatibilizer, a coupling agent, a processing adjuvant, a scorch suppressing agent, and a halogenated resistance. Burning agent. In a second specific embodiment, the present invention is a method for producing a composition of the first embodiment, which comprises at least one (1) acetonitrile polymer having a density of 0.910 g/cc or more. And (ii) an ethylene polymer having a density of less than 0.910 g/cc 20 , (iii) a vinyl decane, (iv) an unfunctionalized flame retardant, and (v) a radical initiator, at least 180° The temperature of C and other steps sufficient to contact the vinyl decane to the polyolefin plastomer or elastomer under contact with the ethylene copolymer. This contact action typically occurs in a 200923005 such as a Banbury mixer or a melt mixer or a extruder of a twin screw extruder. [0017] In the third specific example, the present invention is a method for manufacturing a coated wire, the method comprising the steps of: (1) comprising the composition of the first Mixing the main batch of cross-linking catalyst, (2) extruding or applying the coating composition onto a wire to form a coated wire: and (3) placing the coated wire in a thirsty curing condition Next, the coating composition on the wire can be crosslinked. [Face] In the fourth specific example, the present invention is a wire coated with the composition of the first specific example. In a variation of this embodiment, the composition will form an insulating ferrule on the 5 kel wire. [Embodiment; 3 light Jk specific you 丨 明 _ [0019] Definition: 15 [Off] Unless otherwise indicated, the numerical range in the disclosure of this case is approximate, and therefore can be included outside the range The value. As long as there is at least a two-unit value between any lower limit and any upper limit, the numerical range includes all of the values and includes the lower and upper limits in increments of -. For example, if the physical, or other properties of the composition of 20 - such as molecular weight, viscosity, swell index, etc. are between 100 and 1,000, it is intended to include, for example, 100, 101, 102, etc. Individual values, and values such as 1 to 144, 155 to 170, 197 to 200, etc., which are explicitly recited. For a range of values containing more than one or containing a fractional number greater than - 200923005 (for example, 1.1, 丨.5, etc.), one of the unit values is appropriately considered to be o.oool, 〇.〇〇ι'ο'οι or 〇.1. For a range of values containing a single number of ten (for example, 1 to 5), one of the unit values is typically 0.1 as a reference. All possible combinations of numerical values between the lower and upper 5 values, which are specific to the specific examples, should be considered as being explicitly described in this disclosure. The numerical ranges provided in the present disclosure are particularly those having a density, a weight and a number average molecular weight, an ethylene content in an ethylene/α-olefinic copolymer, a relative content of a composition in a mixture, and Various different temperatures and other processing parameters. [0021], a line ', a source cable', and the like terms are used to refer to a guide, a spring, or the like of a protective jacket or an outer surface, such as an optical fiber line, etc. Typically The rule line is typically two or more wires or fibers that are connected together in a common protective jacket or circumstance. The individual wires or fibers in the outer 15 sets may be bare wires. The typical material design is described in SAE J-1128 and iS〇j 〇〇 Polymer '' represents a compound prepared by polymerization whether it is the same or different types. The generic term of the polymer 20 is generally used to refer to the term "homopolymer, which is polymerized with only one type of monomer", and as follows, 'knife polymer or copolymer.' [0023] The polyterpene polymer of "?" represents a unit comprising ethylene derived from the unit (the molar polymer typically contains at least 50 mole percent, and the unit is self-bounding. 10 200923005 [0024] "heteromeric polymer" and "copolymerization "" means a polymer prepared by polymerizing at least two different types of monomers. These collectively include a typical copolymer (i.e., a polymer polymerized from two different types of monomers) and Polymeric materials (eg, terpolymers, tetrapolymers, etc.) prepared by polymerizing more than two different types of monomers. [0025] "Polyolefin" and similar terms mean that one is derived from, for example, a polymer of a simple olefin monomer of ethylene, propylene, 1-butene, 1-hexene, 1-hexene, 1-octene, and the like. The olefin monomers may be substituted or not. Substituted, and if substituted, the substituent may be substantially altered. For the purposes of the present invention, the substituted olefin monomer comprises VTMS, vinyl acetate, C2-6 alkyl acrylate, conjugated And non-conjugated dienes, polyolefins, carbon monoxide and acetylenic compounds. Many polyolefins are thermoplastic and may include a rubber phase for purposes of the present invention. Polyolefins include, but are not limited to, polyethylene, polypropylene, Polyiso Butene, 15 polyisoprene and various different heteromolecular polymers thereof; polyvinyl acetate; polyacrylate and polymethacrylate; polyvinyl decane and the like. [0026] "Compound", "polymeric blend" and like terms mean a blend of two or more polymers. This blend may or may not be added to 20 to mix. This blend may It may or may not be phase separated. This compound may or may not contain one or more regional structures as determined by tunneling electron spectrum, light scattering, X-ray scattering, and any other means. 200923005 [0027] "Pentane-grafted ethylene polymer" and similar terms are represented by grafting a monodecane functional group onto the polymer backbone of the ethylene polymer, such as described in USP 3,646,155 or 6,048,935. A decane-containing ethylene polymer prepared by the method. [0028] "Composition" and like terms mean a mixture or blend of two or more components. In the inclusion of a mixture or blend of materials used to prepare the decane-grafted polyolefin, the composition comprises at least one ethylene polymer having a density of at least 0.910 g/cc and a density of less than 0.910 At least one ethylene polymer of g/cc, an untreated flame retardant, monovinyl decane, and a radical initiator. In the contents of a mixture or blend of materials used to prepare a cable sheath or other article, the composition includes all of the components of the mixture, for example, ethylene grafted with decane. Polymers, non-halogenated flame retardants, and any other additives such as curing catalysts, lubricants, fillers, antioxidants, and the like. [0029] The "catalytic content" is representative of the amount required to promote the reaction of the two components at a detectable level, which is preferably a commercially acceptable level. [0030] "and" is used to mean that the polymer has less than or equal to 90 weight percent 20 to extractable xylene or decahydronaphthalene (i.e., greater than or equal to before or after being formed into an article). 50% by weight of gel content. [0031] "cured" and similar terms mean that the polymer will or will be exposed to cross-linking before or after being formed into an object. deal with. 12 200923005 [ο ο3 2 ] "crosslinkable" and similar terms mean that the polymer is not cured or crosslinked before or after being formed into an object and has not been subjected to or exposed to a substance. Treatment of cross-linking, although the polymer may contain additives or functionalities that would result in substantial cross-linking when subjected to or exposed to this treatment (for example, 'exposed to water') base. 1〇〇33] ethylene polymer: [〇〇34] regardless of the term representing the ethylene polymer ("first ethylene polymer") having a density of 0.910 g/cc or more, or representing a density of less than 10 0.91 g/cc of the ethylene polymer ("second ethylene polymer"), the ethylene polymer may be homogeneous or heterogeneous. The homogeneous ethylene polymer typically has a range from 1.5 to 3.5 Dispersibility (Mw/Mn or MWD), and is essentially uniform comonomer distribution, and is measured as a single relatively low by a differential scanning calorimeter (DSC) The melting point is characterized. The heteropolyethylene polymer typically has a MWD greater than 3.5 and lacks uniform comonomer distribution. Mw is defined as the weight average molecular weight, while Mn is defined as the number average molecular weight. The demon w is a technique that is measured by the technique: the 20 polymer is based on a linear linear mixing bed (Polymer Laboratories) with a temperature of 14 G ° C. W plus 丨 丨 高On the temperature chromatography unit, the gel permeation layer hiding (GPC) was used for analysis. The weight of the sample was prepared by using 1,2,4-trichlorobenzene as a solvent for injection. u milli 13 200923005 liters per minute (mm/min), and the injection volume is 100 microliters (μΐ). The molecular weight is measured by using narrow molecular weight distribution polystyrene standards (from Polymer Laboratories) and Calculate the volume of the levee, which is based on the appropriate Mark-Houwink coefficient of polyethylene and polystyrene (as by Williams and Ward).

Journal of Polymer Science, Polymer Letters, Vol. 6, (621) 1968, which is hereby incorporated by reference for all of its entireties in the the the the Ethylene)b 10 In this equation, a = 0.4316 and b = l. The weight average molecular weight, Mw, is calculated in accordance with this equation in the usual manner:

Mw = E (wi) (Mi) where % and the take-up are the weight fraction and molecular weight of the i-th portion from the Gpc column, respectively. Typically, the Mw of the heteromolecular polymer elastomer is from 10,000, preferably 2 Å, _, more preferably 4 Å, 嶋, and especially 60,000 to _, _, preferably 5 Å. 〇〇, more preferably only 200,000, and especially 15 〇〇〇〇. Low or high pressure processes can be used to produce the first or second ethylene polymer. They can be produced by conventional techniques in a phase-to-phase process (which is a solution or a process). The low press process is typically carried out at a pressure below the square inch psi", and the high pressure process is typically carried out at a pressure of 15,000 pSi. [(10)37] A typical catalyst system for the preparation of each ethylene polymer, including a catalyst based on magnesium/titanium (10), a catalyst based on the system 14, 200923005 system, a chromium-based catalyst system, Metallocene catalyst systems, constrained geometry catalyst (CGC) systems, and other transition metal catalyst systems. Many of these catalyst systems are commonly referred to as Ziegler-Natta catalyst systems or Phillips catalyst systems. An effective catalyst system includes a catalyst using chromium or molybdenum oxide on a ceria-alumina support. [0038] Efficient ethylene polymers include low density homogeneous polymers of ethylene produced by high pressure processes (HP-LDPEs), linear low density polyethylene (LLDPEs), very low density polyethylene (VLDPEs), ultra low 10 density polyethylene (ULDPEs), intermediate density polyethylene (MDPEs), high density polyethylene (HDPE), metallocene copolymers, and units containing acrylic acid and / or alkyl acrylate and / or methacrylate Ethylene copolymer. [0039] The high press schedule is typically a free radical initiated polymerization and is carried out in a tubular reactor or a stirred autoclave. In the tubular reactor, the pressure system falls within the range of 25,000 to 45,000 psi, and the temperature falls within the range of 200-350 degrees Celsius (°C). In the stirred autoclave, the pressure system falls within the range of 10,000 to 30,000 psi, and the temperature falls within the range of 20 to 175-250 °C.

The VLDPE or ULDPE may be a copolymer of ethylene and an α-olefin having one or more of 3 to 12 carbon atoms and preferably 3 to 8 carbon atoms. The density of the VLDPE or ULDPE may fall within the range of 0.870 to 0.915 g/cc. The melt index (MI 15 200923005 or l2) of the VLDPE or ULDPE may fall within the range of 0.1 to 20 grams (g/10 minutes) per 10 minutes and the car is preferably 0.3 to 5 g/10 minutes. Within the scope. The VLDPE or ULDPE portion of the comonomer based on the weight of the U 6 copolymer in addition to ethylene may fall within the range of i to 49 weight percent (four)%) 5, preferably 15 to 4〇 plus % of the range. [乙41] The ethylene polymer entangled in the practice of the present invention may comprise units derived from three or more different monomers. For example, a third comonomer may be another alpha-dilute hydrocarbon or one such as ethylene norbornene, butadiene, 1,4-hexanedisulfide or dicyclopentadiene. Rare class. Ethylene/propylene 10 copolymers are usually referred to as ruthenium rubber or simply as EpRs, while ethylene/propylene/two red sakis are a EPDM. The third comonomer may be present in an amount of from i to 15% by weight based on the weight of the copolymer, and preferably it is! It is present in an amount of up to 1% by weight. Preferably, the ethylene polymer comprises units derived from two or three comonomers comprising ethylene 15. _2] M LLDPE can include VLDpE uLDpE and MDPE which are also linear, but they usually have a density falling within the range of 〇·916 to 925 925_. It may be a copolymer of - (tetra)thene having from -3 to 12 carbon atoms and preferably from 3 to 8 carbon atoms. The melt 2〇 index is measured in Α8ΤΜΙΜ238 (19 (^/2·16 kg), and 1 is in the range of 1 to 20 g/H), preferably 3 to 8 g/ Within 10 minutes. [0〇43] The density of the ethylene polymer is based on ASTM D-792, and the first ethylene polymer (i.e., those having a line of 16 200923005 prior to grafting is 0.9 i〇g/cc). Or a greater density), these densities range from a minimum of 〇910°, preferably 0.913 and more preferably 0.915, g/cc to typically a maximum of 0.965, preferably 〇·93〇. More preferably, it is 926.926g/cc. While the second ethylene polymer (i.e., those having a density of less than 5 〇 _ 91 〇 g / cc prior to grafting), these density ranges are from a minimum of 0.850, preferably 0-870 and more preferably. The ground is 880.880, g/cc to typically at most 〇.908, preferably 0.907 and more preferably 0.905 g/cc. [0〇44] More specific examples of the ethylene polymer used in the present invention include ATTANEtm (-ethylene/1-octene ULDPE) both manufactured by The Dow Chemical Company Limited, Inc. FLEXOMERtm (-ethylene/1_hexene VLDPE); homogeneously branched linear ethylene/α-dilute hydrocarbon copolymer (for example, TAFMERtm from Mitsui Petrochemicals Company Ltd. and EXACTtm from Exxon Chemical Company); homogeneously divided The branch is substantially linear 15 ethylene/α-olefin polymer (for example, AFFINITYtm plastomer and ENGAGEtm elastomer available from The Dow Chemical Company); INFUSEtm (available from The Dow Chemical Company) Obtained ethylene/1-octene multi-block copolymer); DOWLEXtm (LLDPE obtained from The Dow Chemical Company 20); PRIMACORtm (ethylene/acrylate copolymer obtained from The Dow Chemical Company) And an ethylene copolymer polymerized by high pressure radicals such as ethylene/vinyl acetate (EVA) (for example, by E.I_Du Pont du Nemours & Co.) Made of ELVAXtm polymer) and ethylene ethyl acrylate (EEA) copolymer (for example, 17 200923005 'AMPLIFYtm EEA functional polymer available from The Dow Chemical Company ^^ ι σj) 0 [〇〇45] A more preferred second ethylene polymer is a homogeneous branch having a melt index of from 0.01 to 1,000, and preferably from 0 to 1 and more preferably from 10 to 10 minutes per 10 minutes. Linear and substantially green ethylene copolymer. The substantially linear ethylene copolymer is particularly versatile and is well described in usp 5,986 028. Typical A A-from--- 5 The first ethylene polymer is a mono-polymer, but - or a blend of 10 15 20-k polyethylene polymers can also be used as the first - with one or both of the second dilute polymers, human, human/, the blend may conform to the polymer density conditions. [0046] The content of the ethylene-thin polymerization in the composition of the present invention is typically 5%, and the blade edge is small and preferably 10% by weight, and the maximum line is typically 70%. 〇/〇, and know that A iL is 1 and the car is preferably 30wt%. Similarly, the minimum content of the -7th vinyl-polymer in the composition of the composition is typically 5 wt%. And preferably 丨 θ is also °, and the maximum inclusion is typically 70wt / ’ ' and preferably 3 〇 n uwt /. . Typically, the total composition of the composition is the first enthalpy of the second remedy A, the olefinic compound, the unhalogenated flame retardant and any = additive) based on the composition of the composition (That is, the combined weight of the (four)•ethylene polymer) is from 3 to 70, from 40 to 60 for the rider and from 45 to 55 wt% for the Venetian. Typically, the bismuth-and second ethylene polymer is present at a weight of between 8 and 1:2, preferably W:G#1:1.8. Between and more preferably " between 1.1 and 1: 丨5. 18 200923005 [0047] Vinyl calcination: [0048] can be effectively grafted to the ethylene polymer, polyolefin plastomer and/or elastomer, and any decane of the ethylene copolymer, or such decane Mixtures can be used to practice the invention. Suitable decanes include those having the following formula: R1 Ο H2C=c—(c-(CnH2n) y)xSiR'_3 wherein R' is a hydrogen atom or a methyl group; X and y are 0 or 1 However, when X is 1, y is 1; η is an integer of 1 to 12, preferably 1 to 4; and each R" is independently a hydrolyzable organic group 10 a group such as an alkoxy group having 1 to 12 carbon atoms (for example, a methoxy group, an ethoxy group, a butoxy group), an aryloxy group (for example, a phenoxy group), and an aralkoxy group. (Benzyloxy), for example, an aliphatic alkoxy group having 1 to 12 carbon atoms (for example, a methyloxy group, an ethyloxy group, a propenyloxy group), an amine group or a substituted amino group ( An alkylamine, an arylamine group, or a lower alkyl group having 15 atoms containing from 1 to 6 carbons, as long as no more than two of the three R" are alkyl groups (for example , vinyl dimethyl decyloxy decane). It is also suitable to use an anthrone having a ketoamine hydrolyzable group such as vinyl tris(nonylethyl ketone amine) decane. The decane which can be used includes a hydrogenohydro acid group containing an ethylenic unsaturated (for example, ethylene, propyl, isopropyl, butyl, 20 cyclohexenyl or γ-(fluorenyl) propylene oxide. Allyl), and an unsaturated decane of a hydrolyzable group (for example, a hydrocarbyloxy group, a hydroquinoneoxy group or a hydrocarbon amine group). Specific examples of the hydrolyzable group include an anthraceneoxy group, an ethoxy group, a methyl methoxy group, an acetate group, a propenyloxy group and an alkyl group or an arylamine group. Compared with 19 200923005, the best stone is characterized by the unsaturated sacrificial oxygen which can be grafted onto the polymers, and the preparation method is more fully described in USP 5,266,627. . Ethylene trimethoxy zeoxime, ethylene triethoxy decane γ-(meth) propylene methoxy propyl trimethoxy decane, and these sinter & The better function of Shi Xizhuo. [clear] the content of the scorpion which is actually used in the present invention may vary depending on the nature of the polymer to be grafted, the sinter, the processing conditions, the grafting efficiency, the end use and A significant change is made by similar factors, but it is typically at least 1, preferably at least 15, and more preferably at least 2 wt%. The sand is burnt. Convenient and economical are generally two major limitations in considering the maximum amount of decane actually used in the present invention, and typically the maximum content of the decane is no more than 6, preferably no more than 5, more The preferred area is no more than 4% by weight. The weight percent decane is in a composition comprising (1) a polyolefin plastomer and/or an elastomer, (U) an ethylene copolymer, (iii) a non-halogenated flame retardant, 15 and a Gv) ethylene base stone. Contains the weight content of Shixia. [0〇5〇] Non-halogenated flame retardant: [0〇51] The flame retardant actually used in the present invention is a hydrated inorganic filler, for example, hydrated alumina (aluminum hydride, Α1 (ΟΗ) 3 or ATH), hydrated magnesium oxide, hydrated calcium citrate, hydrated magnesium carbonate, or the like. These hydrated inorganic fillers can be used alone or in combination with one or more other hydrated inorganic fillers, which are more fully described in U.S. Patent 4,732,939. Hydrated alumina (ATH) is generally used as a flame retardant and is a preferred flame retardant which can be used in one of the present inventions. The hydration chemical bond of the moisture from the key to the e-filled inorganic filler is released when the plastomer or the ruthenium ethylene copolymer is burned or ignited to absorb heat, so that the resistance is guided by the set of wires Or, for example, a coated wire consisting of the composition of the article. Although it may diverge in the case of a thief, 'S #x佳' may also have a smaller amount of filler containing the _chemical flame retardant. The size of the filler should be similar to that of the other components of the composition, which are typically used in the art. Flame retardant compositions may contain other flame retardant additives, Example 10 15 20 Carbonic acid, red fill, Shi Xi stone, oxidized Shao, trioxide, talc, sticky, no machine repair clay, zinc, trioxide, _ stone, cloud::: Saki, (10), her Purpose, hindered amine stabilizer, octaammine, / compound and expandable graphite. The minimum content of the un-fired flame retardant in the composition of the present invention is, and the type is 30, preferably 4 〇 Wt%, and the maximum content is 70. Preferably, it is 6 〇 milk %. 100531 radical initiator: 'diterpene vinyl group, grafted in the presence of a radical initiator (eg, a compound or an azo compound) At the time, by the method of Ren Qiang or by ionizing radiation or the like, grafting to the plastomer, the ethylene copolymer, and any of the substances present in the group. Odor diisobutyl The organic starting agent is preferably, for example, any of the initiating agents, for example, hydrogen peroxide, red butyl peroxide, triterpene formic acid, third Butai vinegar, 匕 匕 笨 笨 笨 、, cumene hydroperoxide, gas nucleus butyl vinegar, methyl _ peroxide, 2,5_m (t butyl peroxy) hexane, 21 200923005 Laurel a base peroxide and t-butyl peracetate. A suitable azo compound is azobisisobutyl nitrile. [0055] The content of the initiator may vary, but it is typically a content of 0.04, preferably at least 0.06 wt%. Typically, the starting agent is not more than 0.15, preferably not more than about 0.1% by weight. The ratio of decane to the initiator may also be Widely varied, but a typical decane: starter ratio is 20:1 to 70:1, preferably 30:1 to 50:1 ° [0056] although any conventional method can be used The decane is grafted 10 to the polymer, although the preferred method is in a reactor extruder (e.g., preferably a single screw having a length/diameter (L/D) ratio of 20: 1 or greater In the first stage of the twin-screw extruder, the polymer is blended and melt-mixed with decane and the initiator. The grafting conditions can be changed, but the melting temperature is based on the initiator. The residence time and the half-life, and typically 15 is between 180 and 280, preferably between 190 and 250 ° C. [0057] The curing or crosslinking of the decane-grafted polymer of the present invention, Accelerated by a curing catalyst that can be used in the present invention and any catalyst that can provide this function These catalysts generally include organic tests, acid repellency, and organometallic compounds including organic titanates and complexes or carboxylates of argon, diamond, iron, 20 nickel, zinc and tin. Specific examples of the catalyst include Dibutyltin dilaurate, dioctyltin maleate, dibutyltin diacetate, dibutyltin dioctoate, stannous acetate, stannous octoate, lead naphthenate, zinc octoate and cobalt naphthenate. For example, laurel Dibutyl acrylate, dimethyl hydroxy tin oleate, dioctyltin maleate, maleicene 22 200923005 di-n-butyltin carboxylic acid tin, and, for example, 2-ethylhexanol The compounds are particularly useful in the present invention. [0058] The amount of the curing catalyst or the mixture of curing catalysts used is the catalyst function 'the system is typically - between 0.01 and 0.1 5', preferably 〇.03 to 〇〇_%. The content between. 100591 The decane grafting of the ethylene polymer: [〇〇6〇1 s ethylene polymer is grafted in the presence of the undentified flame retardant in § 矽 矽. The ethylene polymer, vinyl decane and free radical initiator are mixed using known equipment and techniques and placed at a level of at least 180', preferably at least 185 ° C up to 210. (: The temperature of the grafting temperature. The mixing equipment is a Banbury mixer or similar mixer, or a twin-screw extruder. The decane graft polymer decane The content is typically between 1 and 3 wt%. 15 Γ〇〇 61] forming the wire coating: [〇〇62] after the ethylene polymer is grafted with decane, the decane is modified The ethylene polymer and the non-halogenated flame retardant are mixed together with a main batch of a catalyst and extruded onto a wire. The main batch of the catalyst contains a large amount of a modified polymer/block with the decane. The flammable agent constitutes a representative portion of the solidified catalyst mixed to form a substantially homogeneous mixture, which is then mixed with the decane-modified polymer and the non-halogenated flame retardant. Other additives such as antioxidants, stabilizers, etc. may also be included. This mixing is usually carried out in an extruder which is then extruded onto a wire or cable 23 200923005, And then shipped A steam bath or water bath, typically operated at 90 ° C, is exposed to moisture. [0063] The present invention is more fully described by the following specific examples, unless otherwise indicated, all parts and The percentage is calculated by weight 5. Specific examples [0064] The following are the materials used in these specific examples: [0065] (1) AFFINITY EG 8200 is a density that can be obtained from The Dow Chemical Company. 870. 870 g/cm 3 and a polyolefin plastomer having a melting index of 5 g/10 min. [0066] (2) AFFINITY EG 8402 is a density of 0.902 g/cm 3 which can be obtained from The Dow Chemical Company and melted. A polyolefin plastomer having an index of 30 g/10 min. [0067] (3) DOWLEX 2035 is a linear density of 0.919 g/cm 3 and a swell index of 6 g/10 min which can be obtained from The Dow 15 Chemical Company. Low Density Polyethylene [0068] (4) AFFINITY PL 1850 is a polyolefin plastomer available from The Dow Chemical Company with a density of 0.902 g/cm3 and a smelting index of 3 g/10 min. 20 [0069 ] (5) AFFINITY KC 8852 is a one from The Dow

Chemical Company obtained a polyolefin plastomer having a density of 885-885 g/cm3 and a melt index of 3 g/10 min. 24 200923005 [0070] (6) ATTANE 4404G is an ultra low density ethylene/octane copolymer which is available from The Dow Chemical Company at a density of 904.904g/cm3 and a melt index of 4g/10 minutes. (7) SI-LINKDFD A-5451 is a decane-ethylene copolymer which can be obtained from The Dow 5 Chemical Company at a density of 922.922 g/cm 3 and a melt index of 1.5 g/10 min. (8) SI-LINKDF DB-5480 is a main polymer comprising a polyethylene catalyst carrier having a density of 〇.93 g/cm 3 and a melt index of 3 g/10 min which can be obtained from The Dow Chemical Company. batch. [0073] (9) DFD B-5410 BK is a major batch of carbon black which can be obtained from The Dow Chemical Company at a density of 1.15 g/cm3 and a carbon black of 40% by weight in polyethylene. (10) MARTINAL OL-104/LE is a trihydrate aluminide produced by Albemarle 15 having an average particle size of 1.2 to 2.3 μm and a surface area of 3 to 5 m 2 /g. (11) MARTINAL OL-104/S is a surface-coated trihydrate produced by Albemarle having an average particle size of 1.2 to 2.3 microns and a surface area of 3 to 5 m 2 /g. Aluminide. The surface coating of this table is decane. (12) HYDRAL PGA-SD White is a trihydrate aluminide produced by ALOCA having an average particle size of 0.95 to 1.3 μm and a surface area of 4 to 10 m 2 /g. 25 200923005 [1377] (13) CYANOX STDP is a thiodipropionic acid double hard S alcoholic vinegar available from Cytec Industry. (14) IRGANOX 1010 or 1010FF is a tetrakis (methylene (3,5-di-t-butyl-4-hydroxyphenylpropionic acid) 5 methane available from Ciba Corporation. [0079] 15) INDUSTRENE 5016 is stearic acid available from Cr〇mpt〇n Chemical Co. [0080] (16) DOW CORNING Z-6518 is a triethyl ethoxylate available from D〇w Corning.基石夕烧. 10 [0081] (17) DOW CORNING MB50-002 is a self-sufficient

Dow Corning obtained a major batch of a high molecular weight polyoxane in a low density polyethylene carrier resin containing 50% by weight of a high molecular weight agglomerated polymer. [0082] (18) TRIGONOX 29-40B PD is a 15% by weight of 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane alkyl. (19) TRIGONOX 101 is a 2,5-dimethyl-2,5-di-(t-butylperoxy)hexane which can be obtained from Akzo Nobel. [0084] (20) VULCUP R is one of available from Geo Specialty

A mixture of meta and para isomers of a, a"-bis(t-butylperoxy)-di-isopropyl 20 benzene obtained by Chemicals. [0085] Tables 1-7 show non-conformities such as Specific examples of comparison of performance requirements specified by SAE J-1128 and MS-8288 (especially in extension and high temperature tests at 150 ° C.) Table 1 shows comparative compound A and comparative compounds containing ATH and polyethylene. The composition of B. These compounds were prepared in a Banbury 26 200923005 mixer (Banbury mixer). After drying, the compound was given in Table 2 (compared with the specific examples I and the comparative examples) The blending ratio was blended with a monodecane copolymer (SI-LINK DFDA-5451) and a major catalyst batch (SI-LINK DFDB-5480), and a 2.5" wear with a helium flow control screw was used. The Weiss standard extruder (l: D is 24:1) was extruded onto a 18 AWG/19 standard copper wire. The insulation thickness was 16 mils (a TXL structure according to SAE J-1128). The extruded wire was cured in a water bath at 90 ° C for 12-15 hours. Test results of the wire It is shown in Table 2. The results show that the comparative example j 10 and the comparative specific example II do not meet the 150 ° C temperature test according to the specifications of Daimler Chrysler MS-8288. The above blending method does not provide sufficient Curing action to pass the high temperature test at 15 ° C. [〇〇86] Table 3 shows the composition of Comparative Compound C containing SI-LINK DFDA-5451 copolymer, a mixture of a poor hydrocarbon plastomer and ATH. A compound system 15 was prepared in a Banbury mixer. After drying, the compound was then combined with a major catalyst batch in the ratios shown in Table 4 (comparative examples). DFDB_548〇) was blended and extruded onto a 18 AWG/19 standard steel wire using a 2_5” Davis standard extruder with a PE flow control screw (L: D 24:1). The line 2 速度 speed is 91 m / min. The thickness of the insulation is 16 materials. The extruded wire is 12-15 hours in the water. The test results of the wire are shown in Table 4. The results show that More specific example m can pass the high temperature test, but it does not match Extensibility requirement. Compared with Comparative Example I and Comparative Specific Example II, the composition can improve the cured state of the completed 27 200923005 compound, but cannot be provided due to the poor filler acceptance of SI-LINK DFDA-5451. Sufficient extensibility. [Table 87] Table 5 shows the composition of Comparative Compound D containing an ethylene-octene copolymer, ATH vinyltriethoxylate, and a peroxide. The 5 components were mixed at 180 ° C in a Banbury mixer to complete the grafting reaction. This compound was then blended with a major catalyst batch in the ratios described in Table 6 (Comparative Example IV) and a 2.5" Davis standard extruder with a PE flow control screw (L) was used. : D is 24: 1) to extrude onto a 18 AWG/19 standard copper 10 wire. The linear speed is 91 m/min. The insulation thickness is 16 mils. The extruded wire is at 90. It was cured in a water bath at ° C for 12-15 hours. The test results of the wire were shown in Table 6. The results show that the comparative example IV can pass the 150 ° C high temperature test, but it cannot meet the extensibility requirement. The ATTANE 4404G decane grafting process can be used to improve the filler acceptance and extensibility of Comparative Example III, but still insufficient to meet the extensibility requirements of SAE J-1128 and Daimler Chrysler MS-8288. [〇〇88] 7 shows a composition comprising a linear low density polyethylene (DOWLEX 2035), a polyolefin plastomer (AFFINITY PL 1850), a peroxide, 20 vinyl triethoxy decane, and a comparative compound E of ATH. At 180°c in a Banbury Mixing was carried out in a mixer (Banbury mixer). The compound was then blended with a primary sinter. The compound was then blended with a major catalyst batch (DFDB-5480) in the ratios described in Table 8. A 2.5" Davis 28 200923005 standard extruder (L: D of 24:1) with a PE flow control screw was used to extrude onto a 18 AWG/19 standard copper wire. The linear speed is 52 m/min. The insulation thickness is 16 mils. The extruded wire was cured in a water bath at 90 ° C for 12-15 hours. The test results of this wire are shown in Table 8. The results show that the ratio of 5 to the specific example V can meet the 150 ° C high temperature test, but it can not meet the extension requirements. This specific example shows an improvement in the extensibility of Comparative Example IV. [0089] Table 9 shows the polyolefin plastomers (AFFINITY PL 1850 and AFFINITY KC 8852) containing two Dow companies, a linear low density 10 degree polyethylene (DOWLEX 2035), ATH, vinyl triethoxy decane and The composition of the compound A1 of the oxide and the compound B1. The ingredients were mixed at 180 ° C in a Banbury mixer to complete the decane grafting reaction. After drying, these compounds were then blended with a major catalyst batch 15 (DFDB_5480) in the proportions indicated in Table 10, and extruded using a 2.5" Davis standard with a PE flow control screw. The machine (L: D is 24:1) was extruded onto a -18 AWG/19 standard steel wire. The linear speed was 69 m/min. The insulation thickness was 16 mils. The extruded wire system It was cured in a 9 (rc water bath for 12-15 hours. The test results of this wire were shown in Table 2〇. The results show that the specific case AA1 and the specific case BB1 are surprisingly wordable - same as '/Jm· It can also meet the requirements of extensibility. High temperature test and compliance with elongation requirements. Study on shelf life stability of compound A1. Surprisingly, it is stored in seal under (4) 29 200923005 • After 7 weeks, the bag will exhibit very good shelf life stability with less than 10% change in flow index. Table 1 Comparison of major batch composition components containing ATH and polyethylene Compound A composition, wt% comparison Compound B composition, wt% A Ffinity EG8200 27.2 0.0 Affinity EG8402 0.0 27.2 Hydral PGA-SD White 70.0 70.0 Cyanox STDP 1.6 1.6 Iraganox 1010 0.8 0.8 Industrene 5016 0.4 0.4 Total 100.0 100.0 Table 2 Cured conductors manufactured in the main batches shown in Table 1 The test results are compared with the specific example I composition, wt% comparison specific example II composition, wt% compound A 71.1 compound B 71.1 Si-Link DFDA-5451 27.2 27.2 Si-Link DFDB-5480 1.7 1.7 total 100.0 100.0 wire test Minimum required tensile strength of J-1128 and MS-8288, MPa 12.5 13.0 10.3 Tensile length, % 406 60 150 Compressibility, kg 3.3 4.3 3.2 High temperature test at 150 °C (MS-8288) By comparing the composition of the main batch composition of Si-Link DFDA-5451, polyethylene and ATH by 30 200923005 Table 3, wt% Affinity EG-8200 3.50 Si-Link DFDA-5451 41.40 Martinal OL-104/S 51.0 Affinity EG-8200 2.5 with a Vulcup R of 0.8 wt% 2.5 Cyanox STDP 1.1 IRGANOX 1010FF 0.5 Total 100.00 Table 4 Made with the compound C shown in Table 3 The test results of the cured wire are compared with the specific example 3 composition, wt% compound c 95 Si-Link DFDA-5480 3 DFDB-5410 BK 2 total 100 wire test the minimum required tensile strength of J-1128 and MS-8288 , MPa 17.2 10.3 Tensile length, % 67 150 Compressibility, kg 4.3 3.2 South temperature test at 150 ° C by comparison of the composition of the main batch of ATH with the copolymer of decane grafted by Table 5 Ingredient composition, wt% 31 200923005

Attane 4404G 40.35 Martinal OL-104/LE 53 Triganox 29-40Bpd 0.15 Dow Corning MB50-002 1.5 Dow Corning Z-6518 3.5 Cyanox STDP 1 IRGANOX 1010FF 0.5 100.00 Table 6 Curing with Compound D as shown in Table 5 Wire test results composition specific example 4 composition, wt% compound D 95 Si-Link DFDA-5480 3 DFDB-5410 BK 2 total 100 wire test J-1128 and MS-8288 minimum required tensile strength, MPa 18.9 10.3 Tensile length, % 77 150 Compressibility, kg 3.4 3.2 High temperature test at 150 ° C by comparing the composition of the composition of the batch containing the decane-grafted copolymer with ATH by Table 75 Composition, wt% Dowlex 2035 20.41 Affinity PL 1850 20.41 Martinal OL-104/LE 53.00 Trigonox 29-40B pd 0.18 Dow Corning MB50-002 1.50 Dow Corning Z-6518 3.00 Cyanox STDP 1.00 IRGANOX 1010FF 0.50 100.00 32 200923005 Table 8 The test results of the cured wire produced by the compound E shown in Table 7 are compared with the specific example V composition, wt% compound E 95 Si-Link DFDA -5480 3 DFDB-5410 BK 2 Total 100 Wire Test Minimum Tensile Strength of J-1128 and MS-8288, MPa 20 10.3 Tensile Length, % 106 150 Compressibility, kg 5.3 3.2 at 150°C The ambient temperature test consists of a composition of the compound A1 comprising the main batch of the copolymer of decane grafted with ATH, and wt% compound B1 composition, wt% Dowlex 2035 15.93 20.74 Affinity PL 1850 15.81 6.00 Affinity KC 8852 10.00 15.00 Martinal OL-104/LE 53.00 53.00 Trigonox 101 0.06 0.06 Dow Corning MB50-002 2.00 2.00 Dow Corning Z-6518 2.00 2.00 Cyanox STDP 0.80 0.80 IRGANOX 1010FF 0.40 0.40 100.00 100.00 Table 10 is shown in Table 9. Test results of cured wires produced by Compounds F and G Specific Example AA1 Specific Example BB1 Composition, wt% Composition, Wt°/o 33 200923005 Compound F 95 0 Compound G 0 95 Si-Link DFDA-5480 3 3 DFDB -5410 BK 2 2 Total 100 100 Wire test Minimum tensile strength of J-1128 and MS-8288, MPa 19.8 21.8 10.3 Tensile length, % 168 172 150 Compressibility, kg 4.1 3.8 3.2 The south temperature test at 150 ° C is passed through the following, although the invention has been described with certain details in the specific examples described above, but the main purpose of these details is to illustrate Explain. Many variations and modifications can be made without departing from the spirit and scope of the invention. All of the documents cited in the above-referenced U.S. Patent, Patent Application Publication, and the entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire disclosure [Simple description of the diagram] (none) 10 [Description of main component symbols] (none) 34

Claims (1)

200923005 X. Patent Application Range: 1. A composition comprising: A. at least one first decane grafted ethylene polymer having a density of 0.910 g/cc or more; 5 B. at least one a second decane grafted ethylene polymer having a density of less than 0.910 g/cc; and C. at least one untreated flame retardant. 2. The composition of claim 1, which comprises at least two second decane grafted ethylene polymers. 10. The composition of claim 1, which comprises from 5 to 70% by weight of the second decane grafted ethylene polymer. 4. The composition of claim 1, which comprises from 5 to 70% by weight of the first decane grafted ethylene polymer. 5. The composition of claim 3, which comprises from 5 to 70% by weight of the first slag-grafted ethylene polymer. 6. The composition of claim 1, which comprises 30 to 70% by weight of the undentified flame retardant. 7. The composition of claim 5, which comprises 30 to 70 wt/hr of the non-halogenated flame retardant. The composition of claim 1, wherein the first and second ethylene polymers each comprise a unit derived from an alpha-dilute hydrocarbon of ethylene and from 3 to 12 carbon atoms. 9. The composition of claim 7, wherein the first and second ethylene polymers each comprise units derived from an alpha-olefin of ethylene and from 3 to 12 carbon atoms 35 200923005. Wherein the ethylene units are the first and second ethylene polymers 1 〇 The composition of claim 1 contains 50% by weight or more of each of these. 5 11. If you apply for the group money of item 9, the (e) and other ethylene units contain 5〇wt% or more of each of the first and second women's polymers. The composition of claim i, wherein the non-halogenated flame retardant comprises a hydrated inorganic filler. 10 13. For the towel, please refer to the composition of item 1, item 1, wherein the un-Methane flame retardant contains a hydrated inorganic filler. 14. The composition for applying for a full-time enclosure, wherein the non-halogenated flame retardant comprises at least one of dihydrate oxide, magnesium oxide hydrate, oxalic acid hydrate, and magnesium carbonate hydrate . 15. The composition of claim 13, wherein the untorped flame retardant comprises at least one of alumina trihydrate, magnesium oxide hydrate, calcium silicate hydrate, and magnesium carbonate hydrate. . 16. The composition of claim 1, which comprises from 4 to 60% by weight of the non-pendant flame retardant. 20. 17. The composition of claim 15 which contains 40 to 60% by weight of the untreated flame retardant. 18. The composition of claim 1, which comprises two or more unhalogenated flame retardants. 19_ The composition of claim 17, which comprises two or more 36 200923005 non-halogenated flame retardants. 20. The composition of claim 1, wherein the first and second ethylene polymers are present in a weight ratio between 1:0.5 and 1:2. 5 21 _ a method for producing a composition as claimed in claim 1, which comprises (1) an ethylene polymer having a density of 0.910 g/cc or more at a temperature of at least 180 ° C And (ii) an ethylene polymer having a density of less than 0.910 g/cc, (iii) a vinyl decane, (iv) a non-halogenated flame retardant, and (v) a radical initiator contact. The method of claim 21, wherein the vinyl decane has the following chemical formula: R1 Ο H2C=C—(c—(CnH2n)y)xSiR"3 wherein R' is a hydrogen atom or a methyl group; x and y are 0 or 1, but when X is 1, y is 1; η is an integer containing 1 15 to 12, preferably 1 to 4; R" is independently a hydrolyzable organic group, such as an alkoxy group having 1 to 12 carbon atoms (for example, a decyloxy group, an ethoxy group, a butoxy group), an aryloxy group ( For example, phenoxy), aralkyloxy (for example benzyloxy), aliphatic decyloxy having 1 to 12 carbon atoms (for example, methyl methoxy, acetam 20 oxy, propyl a decyloxy group, an amine group or a substituted amino group (alkylamine, arylamine group), or a lower alkyl group having 1 to 6 carbon atoms, as long as the three R" Not more than two are alkyl groups (for example, vinyl dimethyl methoxy decane). 37 200923005 23. A method for producing a coated wire, the method comprising the steps of: (1) the composition of the first specific example and the composition comprising the first item of the patent application scope And mixing the main plates of a cross-linking catalyst to form a coating composition, (2) applying the coating composition to the 5-wire to form a coated wire, and (3) coating the coating The wires of the layer are placed under moisture curing conditions such that the coating composition on the wire can be crosslinked. 24. A wire which is coated with a composition as in claim 1 of the patent application. 10. The wire of claim 24, wherein the coating is in the form of an insulating sheath. 38 200923005 VII. Designation of representative representatives: (1) The representative representative of the case is: (). (None) (2) A brief description of the symbol of the representative figure: 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: